Basic cooroson related to Sugar industry

NHNG KHI NIM C BN V N MN TRONG H THNG NI HI NH MY NG 1. nh ngha n mn 2. Cc dng n mn thng gp trong h thng ni hi n mn xy n mn axit: Ha tan lp bo v magnhtit trong h thng ni hi, xy ra trong h thng c c v trn ng ng nc ngng 3. Trng thi n mn thp khng g v cc dng n mn: n mn l (ni c dc thp khng g) n mn ng lc n mn khe (crevice corrosion ) i vi ni c c nong ng n mn mi mn do dng chy Mt s vn lin quan n hn thp khng g

4. n mn ng 5. n mn di lp cn

Corrosion is the reaction of a metallic material with its environment that results in a damage of the material or component before its regular lifetime. Corrosion effects are mostly the result of electro-chemical reactions, but mechanical influence is possible too. Attention: All materials used for technical components or constructions have a defined not endless lifetime only. The lifetime is supposed to be approx. 5-50 years, depending on material, design, environment and operation conditions.

1. nh ngha n mn l phn ng gia vt liu kimloi v mi trng gy nn s ph hy vt liu hoc chi tit sm hn tui th thng thng ca n. Qu trnh n mn trong ni hi ch yu l n mn in ho. l phn ng gia vt liu kim loi vi mi trng m hu qu l vt liu hoc cu kin b ph hu

Vng m kim loi b n mn v i vo dung dch di dng cation kim loi (nh ion Fe2+) gi l ant. Vng m mi trng xung quanh - hu ht l nc- phn ng vi in t t ant chuyn n gi l catt. V d nh phn ng kh xy (O2) thnh anion OH- (dng n mn xy) hoc cation H+ ca axit b kh thnh nguyn t hyr (dng n mn hyr). ant catt n mn xy n mn axt: O2 + 2H2O + 4e = 4OH2H+ + 2e = H2 Fe 2e = Fe2+

S in hnh ca qu trnh n mn xy trn st/thp c a ra trn hnh .

Hnh : S nguyn tc n mn xy. Corrosion Rate Tc n mn c o bng s tn hao trng lng tnh theo mm/nm hoc tn hao trng lng trn mt n v din tch b mt sau mt thi gian nht nh g/m2gi g/m2ngy, g/m2nm
A uniform material loss < 0.1 mm/yr (or mm/a) is defined as technical corrosion resistant for common use.

For instance low-alloyed carbon steel at operational temperatures of 300-330 C in low conductive alkaline water or steam shows a corrosions rate of approx. 0.15 mm within 20 years, that of austenitic stainless steel is approximately ten times lower! Most of corrosion rates from literature are measured under laboratory conditions for uniform corrosion and are not direct transferable to a technical application. A little corrosion rate as mentioned excludes not other specific corrosion effects, like stress corrosion cracking (SCC), flow assisted corrosion (FAC), strain induced corrosion or crevice corrosion etc.!

2. Cc dng n mn thng gp trong h thng ni hi Trong ni hi, dng v tc n mn c quyt nh ch yu bi trng thi khc nhau ca lp magnetite bo v (nh lp xp hay lp chc c), khuyt tt trong lp magnetite hoc iu kin thng kh khc nhau ca lp magnetite (trn v di lp cn, trn v di ng mc nc). Trong thc t, d nc cp (BFW) v nc ni (BW) c cht lng tt nht vn khng th trnh khi vt ca cc cht nhim bn nh cc cht khng bay hi (cha trong nc) v c bit l s tun hon cc hp cht kim loi (sn phm n mn) nh hp cht ca st, ng, km dng khng ho tan (cc ht xit) v cc cht rn ho tan. c bit, trong qa trnh khi ng ni hi, cc cht nhim bn thng c hm lng ln hn nhiu, c bit l cc hp cht ca st. Theo l thuyt, dn thp nht ca nc tinh khit 250C khong 0,055 S/cm, ngha l BFW cht lng tt vi dn axit 250C l 0,15 S/cm vn cn cha cc cht nhim bn c dn tng ng 0,1 S/cm. Cc cht nhim bn c th c do cc ngun sau: CO2 ho tan t: Khng kh (ti cn bng t ti 0,6 S/cm). Phn ng phn hu xc ng vt (c trong nc) bi xy, v d nh carbohydrazide. Hi axit hu c t: S thu phn v xy ho cc hp cht amin. Phn ng phn hu cc hp cht hu c.

Hi hp cht amin: khng hon ton b gi li thit b trao i cation. Cc axit v c khng bay hi t: Cc hp cht c trao i ti thit b trao i cation (cc cht ny tri qua thit b kh khong v/hoc tri qua thit b lm sch nc ngng). T axit. 2.1. n mn xy S n mn xy thng xy ra trong sut qu trnh dng l (nu p sut bng khng v hi c thay th bi khng kh). Hin tng ny lm cho thp b n mn cc b (hnh 3 v 4), ging nh thp cacbon b n mn trong kh quyn.

Hnh 3. n mn xy trn ng la ca ni hi Hnh 4. n mn xy trn ng khi.

2.2. n mn axit n mn do axt cacbnic thng xy ra trong ng ng dn hi v trong ng ng nc ngng, (nh 5 v 6). Trong ni hi v trong ni c c nu hm lng axit hu c cao, n mn axit cng c th xy ra

Hnh n mn axit cacbonic trn ng hi lu nc ngng (bn phi: nh phng to). Kim loi d b n mn v b n mn vi tc cao trong mi trng axit

Hinh: Tc n mn thp trong nc 3100C ph thuc vo pH v nng ca HCl v NaOH

n mn cc b n mn di lp cn n mn cc b ti cc vng bc hi ca ni hi vi s truyn nhit ln l do s ng cn ca sn phm n mn, trc ht l lp xit st kt ta t BW, sau n kt hp ti ch vi nc ni hi khng theo mt quy lut no. Ti nhng vng c dng nhit ln, lp cn xp u tin (ging nh bt bin) c to thnh t cn cht rn khng tan sa lng. Cc nhim bn ho tan trong BW chui vo bn trong cc l ca lp cn xp ny, tch t, c c li. V vy m vt liu b ph hu hoc l do pH thp (do tnh axit ca nc ni hi, v d nc lm mt b ln vo nc BW), hoc do pH cao (cn li sau qu trnh ra kim, hay do b thng nn kim lt vo). n mn l n mn cc b dn n to thnh cc l nh c ming l h hoc b bt kn. n mn cc b trong ni hi c th xy ra khi mt vng rng ca lp oxyt bo v b nhng khuyt tt nh di tc ng c hc hoc ha hc. Khi , nu nhn ton b b mt th c v hon ton tt nhng thc cht, s tn cng cc b c th xuyn thng b mt v gy nn r g. Dng in hnh ca n mn l l n mn oxy i vi thp cacbon (ming m), s tn cng ca in Cl- i vi thp khng g austenit (ming kn), n mn ng trong dung dch trung tnh c hm lng sunfat cao (ming kn), s kt ta cc kim loi dng hn trn nn st, n mn nhm hoc km trong dung dch trung tnh hoc axit (ming h). n mn nt/n mn di lp cn n mn nt ch yu gy nn bi n mn tip xc do chnh lch nng ti cc khe nh hoc cc vt nt, v d di lp oxyt, khe ca cc ming m, cc c vt lp rp v.v do s khc nhau v iu kin ha hc bn trong lng v bn ngoi khe. n mn nt thng l nguyn nhn ban u dn n n mn l i vi thp khng g, nu nh lp oxyt mi hn khng c lm sch y . n mn do ng cn cc b hu ht u lin quan n dng n mn khe v iu kin thng kh bn di lp cn v xung quanh n l khc nhau.

C hai dng n mn ni trn u xy ra ch yu l do s khc nhau v nng xy: thp - bn trong khe/di lp cn, cao - bn ngoi khe/xung quanh vng cn.

4.1.1

Carbon Steel and Cast Iron/Steel

Pure iron is too soft for technical constructions and became therefore alloyed with various elements. Most common alloying element is carbon to increase strength and harden ability. In cast iron, the carbon content may rise up to 5 %. Other common alloying elements for low- alloyed steel are aluminium, chromium, copper, manganese, molybdenum, nickel, nitrogen, phosphorous, silicon, vanadium and tungsten (wolfram). As far as the content of these alloying elements do not exceed 8-10% (some contents are much lower), their corrosion behaviour is basically same if oxygen (air) and water (moisture) of the atmosphere is present. The corrosion resistance of weathering steels is up to 5 times better than other carbon steel, but all the low alloyed steels became not passive on humid air - in contrast to the higher alloyed stainless steels. In air and in presence of humidity above 60 %, these types of steel corrode (rust) by formation of iron oxide-hydrates (yellow brown) or iron oxide (simplified hematite, dark brown). This type of corrosion is called atmospheric corrosion or oxygen corrosion. Most constituent of low-alloyed (ferritic) steels are added to obtain specific mechanical properties, such as high strength, temperature resistance, hydrogen resistance, harden ability, low temperature applicability etc. and have only limited influence to its corrosion resistance. Exception is an elevated chromium content that result in significant better resistance to oxidation at elevated temperatures and erosion corrosion (FAC).

Kh nng chng n mn ca thp cacbon v thp hp kim thp ph thuc rt nhiu vo s hnh thnh v duy tr lp xyt t bo v. Lp ooxxyt ny bao gm ch yu l magnetite v hematite v d b ha tan trong mi trng axit, thm ch c axit yu nhit thng (tr axit sunfuric>90%) v trong dung dch kim mnh nhit cao. Trong nc gi tr pH ti u l 9.5 -11.5 ty thuc vo nhit

pH trong khong 12 - 12,5 nhit phng s gi cho thp th ng khi c mt xy, nhng trong mi trng c dn cao(>1000 S/cm) th n mn l c th xy ra Thp cacbon thp nhy vi gy n mn do ng lc khi chu mt ng sut ko cao (gn gii hn chy) khi c mt kim, vi d >4% ung dch NaOH, c bit l nhit cao. Dung dch nitrrat pH axit (v d nc ngng t bn la) cng gy SCC. Thp cacbon v thp hp kim thp c dng rng ri ch to cc chi tit thit b ni hi. Thp cacbon c th s dng n nhit 400 C, nhit cao hn 540 C, ngi ta thng dng thp hp kim c cha Mo v Cr. i vi b qu nhit v b n nhit cc thp hp kim vi hm lng Cr cao hn c th chu ng ti 560-600 C. nhit cao hn na cn s dng cc thp austenit c cha Ni-Cr.hoc thep duplex Thp khng g Thp khng g c dng rng ri cho cc vt liu kt cu chu n mn cao. Nhm vt liu ny bao gm nhiu loi hp kim khc nhau c ch to cho cc ng dng ring bit. Tt c cc loi thp khng g u khng b n mn trong mi trng kh quyn bnh thng nhng khng phi l hon thon bn n mn trong mi iu kin bn n mn ca thp khng g l c mt mng xyt c hnh thnh ngay lp tc khi tip xc vi khng kh/xy trong mi trng m hoc mi trng xy ha. Mng th ng ny cha xyt crm v oxyt st v rt mng, thng khng nh thy ddwwocj bng mt thng tr khi nung nng >300oC. Trong mi trng ion Cl- c bit trong mi trng axit mng th ng ny b ph hy v dn n n mn l. Dng n mn ny se tr nn nghim trng khi trn mt din tch rng ca mng th ng c mt s khuyt tt vi din tch rt nh. V d, ng hn khng cht lng v cc vy hn khng c lm sch k cng. Lp xyt mu xanh v mu en ti mi hm phi c ngn chn bng cch dng kh tr hoc loi b c hc hoc ty trong hn hp axit HF-HNO3 chng n mn l.

Tt c thp khng g u bn n mn oxy nhit cao ti 700 C nhng chng c bn ko thp v hm lng cacbon thp. Thp mactensit v thp duplex c bn cao hn. Thp austenit cha it nht t 6-26% Cr 6-22 % Ni vi cc hm lng c khc nhau. - Thp cacbon thp (< 0.04 % C) c bn thp nhng rt d hn Austenitic stainless steels contain at least 16-26 % chromium and 6-22 % nickel with different carbon content. Thp c hm lng cacbon 0.04 % C khng c cc nguyn t hp kim ha Ti, Nb hoc Ta c th rt nhy cm khi hot ng trong mt thi gian di nhit 450-800 Cdo hn thiu kinh nghim hocdo x l nhit. S nhy nhit dn n s tao thnh cacbit crm trn bin hat v lm cho crm thot ra vng k bin ht v kt qu l xy ra s n mn gia cc bin ht trong mt trng xm thc. S nhy nhit ny c th trnh c nu hm lng C<0,04% (thp cacbon thp) hoc tng bn nhit bng cch thm vo mt lng ln Ti, Nb hoc Ta. hn thp austenit bn nhit th vt liu hn cng cn l vt liu bn nhit vi s c mt ca Nb.
Thp khng g austenit rt bn n mn vi axit nitric hoc cc axit yu khc, dung dch trung tnh, dung dich kim yu v cc ha cht c tnh xy ha min l trong cc dung dch khng cha qu nhiu cc hp cht ca clo, brm, it. Thp khng g austenit rt nhy vi n mn l v n mn ng lc gy nn bi clo, brm, it, thm ch c khi chu mt ng lc ko thp (v d mi hn), c bit l khi nhit >50oC, thuy nhin h hng cng c th xy ra nhit thp hn. Tng hm lng mlipen trogn thp s lm gim s nhy n mn l v ng lc nh trn. NaOH hm lng >4% s gy nn n mn ng lc khi vt liu chu ng sut trung bnh v cao. Thp austenit hp kim ha cao s bn n mn vi cc axit mnh nh axit sunfuric v phtphoric khi khng c mt lng qu ln ion Cl-.

Thp khng g ferit cha 12-30% Cr voi hm lng C < 0,2% Ferritic stainless steels contain 12-30 % chromium with carbon content < 0.2 %. C hp kim ny c tnh do v bn ln nhng khi hn v x l nhit cn phi cn thn trnh nt nng. Cc loi thp ny c trng thi n mn tng t thp austenit nhng bn n mn ng lc khi c mt clo, brm, it trong mt khong rng hn. Stress Corrosion Cracking (SCC), S hnh thnh vt nt (trn bin ht hoc xuyn ht ty thuc vo kim loi, mi trng v ng sut) trong s c mt ng thi ca kim loi nhy vi SCC, mi trng c kh nng 9

gy SCC v ng sut ko. ng sut ny c th c to nn trong qu trnh ch to, gia cng ngui, hn hoc vnh hnh. Hu ht SCC u phi tri qua mt thi gian bnh vi gi hoc vai ngy, nhng vt nt th lan truyn rt nhanh. Cc trng hp in hnh dn n SCC l: - Thp khng g austenit trong mi trng ion Cl- ngay khi chu mt ng sut ko thp - ng thau trong hi ammoniac hoc dung dch cha ion amni. - Thp cacbon trong dung dch >4% NaOH chu ng sut ko cao (gin kim). Hu ht SCC trn thp khng g austenit v ng thau u bt u t nhng l n mn rt nh trn b mt hoc nhng khuyt tt trn lp bo v. n mn ng lc dn n: cc vt nt hnh nhnh cy theo bin ht. Trong nhng iu kin c bit, vt nt xuyn ht cng c th hnh thnh 3.7 Stress Corrosion Cracking (SCC)

Gy n mn do ng lc ch xy ra khi c mt ng thi 3 yu t sau y: Kim loi nhy SCC, Mi trng c th gy SCC i vi kim loi v ng sut ko (to nn trong qu trnh ch to, gia cng ngui, hn hoc vnh hnh) nu thiu mt trong ba yu t trn th SCC khng xy ra Cc trng hp in hnh Thp khng g austenit, c bit l thp Cr-Ni khng cha Mo trong mi trng Cl-, Br-, I-, c bit l pH thp, nhit > 50C, SCC xy ran gay ng sut thp. Thp khng g austenit hoc ferit trong mi trng NaOH > 4-70% nhit cao Thp cabon trong mi trng NaOH > 4-70% (gin kim) ng sut ko cao (gn vi im bn chy) v nhit cao Thp cabon trong dung dch cha nitrat hm lng cao vi pH vng axit ng thau trong hi ammoniac hoc dung dch cha ion amni, ngay khi ch c vt. SCC in hnh u phi tri qua mt thi gian bnh vi gi n vi tun, ty thuc vo iu kin mi trng (ng sut v nng dung dch) dn n gin t ngt hu ht l do nt trn bin ht v vt nt lan truyn rt nhanh.

10

n mn mi mn hoc n mn do dng chy (FAC) v n mn xi mn (cavitation) c hai u ch yu chu nh hng ca iu kin dng chy.

FAC c th quan st thy ch yu trong bm v cnh bm cng nh trong ng nc v van do kt qu ca pH qu thp kt hp vi dng chy tc ln, xem hnh 7.

Hnh 7. n mn mi mn trong mt khi van hi c dng nh van iu chnh .

n mn xi mn l kt qu ca s to bong bng hi v s n tip theo hng vo thnh ng ca chng (c th nghe thy r rt). V d nh trn nh ng ngng cha hn hp nc ngng v hi, xem hnh 8, hoc bm ang vn hnh trong nc nng hoc p sut nng ln ti u vo ca bm u thy r vn ny.

11

Hnh 8. n mn xi mn trn nh ng (v tr 12h) ca ng ngng hi lu.

St v ng Hp cht st trong BFW kim ho c th b ho tan (v d trong trng hp n mn hoc n mn mi mn do dng chy [FAC] trong ng ng cp nc cho ni hi) v khng b ho tan dng ht xit nh. Trong mi trng kim nng ca BW, hu ht hp cht st tn ti di dng cc ht xit khng tan v dng nc tun hon lm cho pH v nhit ca BW ln hn ca BFW. Ngc li vi st, phn ln hp cht ca ng ho tan trong nc, c bit l khi c mt amoni v amin. Gii hn hm lng ca c hai nguyn t ny ch c a ra cho BFW bi v i vi BW s rt kh ly c mu nc thc s i din m trong c c nhng ht nh khng tan. Thnh phn ca chng trong nc BW dao ng mnh, n ph thuc vo ph ti ni hi hoc s thay i p sut v iu kin ly mu (v d: vt liu lm ng, tc dng chy, s khuy, s sc nc ) n mn mi mn/n mn do dng chy (Flow Assisted Corrosion - FAC) n mn mi mn hay n mn do dng chy xy ra khi c mt mi trng nc hoc kh (v d nh khng kh, kh nhin liu, hi) chuyn dch vi tc ln, lm mt i lp bo v ( hon thin hoc mi to thnh) nhanh hn vic to

12

thnh lp ny. Nhng dng chy c hai pha nh: kh v tro, nc v ct, hi v cc git nc nh, nc v nhng bt kh (hi) l nhng mi trng rt nguy him. Mi trng nc - hi (hai mi trng sau cng) c th l nguyn nhn gy nn h hng do va p cng hng hoc to l ging nh phun ct. Thp s b n mn mi mn trong mi trng kim yu (pH < 8,5 - 9) khi tc dng chy > 8 - 10 m/s, c bit l nhit khong 1500C v khng c xy. Tng pH v khng ch nng xy khong 15 - 30 ppb s lm gim nguy c ph hu do FAC (hnh 8). Tng thnh phn Cr trong vt liu cng lm gim tc hi ca FAC (hnh 9). Cc kim loi d b tc ng ca n mn mi mn l nhng kim loi c lp bo v mm nh ng v nhm. Khi ng v nhm lm vic trong mi trng khng n mn th tc dng chy cc i ti mt vng no phi < 1,6 - 1,8 m/s. B mt b mi mn th-ng t-ng i bng, khng c sn phm n mn v c nhng mt phng (cu trc trng ging nh- cn ct).

13

Hnh 8. nh h-ng ca nhit n: a) Tc tn hao thp ccbon VK trong n-c kh ion ti pH 8,5 (NH3) khi c xy v khng c xy (-ng lin nt). b) Tc mi mn thp ccbon VE trong n-c kh ion ti pH 9,05 v nng xy c(O2) < 0,006 mg/kg (-ng t nt). c) Nng Fe2+ tnh ton trong n-c kh ion pH khong 8,7 (NH3) cn bng vi magnetite khi p sut ring ca hyr l 1 bar (-ng nt t c chm).

14

Hnh 9. nh h-ng ca tc dng chy n l-ng vt liu b mt i trong qu trnh n mn mi mn (p = 40 bar, = 1800C, pH = 7, c(O2) 0,05 mg/kg).

15

Mt ni hi c thit k tt s t tui th ti a khi v ch khi thp ni hi c kh nng to thnh v duy tr mt lp xit st mng c kh nng bo v (chnh xc l gm ba lp xit khc nhau) c thnh phn chnh l magnetite Fe3O4(hnh 1a & 2). Mt lp magnetite c tnh cht bo v thc s phi c cu to rn chc, gn nh- khng c l r v bm chc vo b mt kim loi.

Hnh 1. Lp hn hp ca xit st trn b mt thp hp kim thp trong hi ph thuc vo nhit : (a)- <5700C; (b)- >5700C.

16

Hnh 2: nh h-ng ca cc nguyn t hp kim ho thp n nhit to thnh FeO trong vy cn

17

Chiu dy ca lp magnetite bo v ph thuc vo loi vt liu, nhit lm vic v thi gian vn hnh. Ng-i ta tnh ton -c sau 100.000 gi (khong 12 nm) bn pha n-c hoc pha hi, i vi thp hp kim thp (21/4 Cr1Mo) nhit thnh ng khong 3500C (p sut khong 125 bar) s hnh thnh lp magnetite c chiu dy t 10 - 15 m, nhit 5000C - khong 350 m (hnh 3 v nh 1). iu kin t-ng t, trn b mt thp cacbon th-ng (v d thp 35.8) lp magnetite c chiu dy ln hn gp 10 - 20 ln. Mt lp xit c chc c chiu dy 300 m nm trn b mt trong ca ng sinh hi s lm nhit thnh ng tng ln t 30 - 40oK.

Hnh 3: Quan h gia tn hao trng l-ng thp hp kim thp b xy ho trong mi tr-ng xy hoc trong hi v thi gian - tun theo quy lut hn hp parabl - tuyn tnh (ch p dng cho vng nhit </= 550oC)

18

nh 1 Lp bo v st cht( r < 5%) gy nh h-ng khng ng k n s trao i nhit nu nh- chiu dy ca n khng v-t qu 0,2 - 0,3 mm (tu thuc vo dng nhit), tuy nhin nu lp oxit c xp ln hn, hoc b tch lp th s gy nh h-ng ti nhit thnh ng (hnh 4). Mt lp magnetite mng c tnh cht bo v l mt lp vy ti cn thit nh-ng phi vi iu kin l n khng b trn ln cc lng ng t BW! Lp sn phm n mn st c xp ln - xem nh 2, lp sn phm n mn b tch lp - xem nh 3.

19

nh 2

nh 3

20

Hnh 4. S ph thuc ca nhit thnh ni hi vo chiu dy lp cn c xp khc nhau: a) 5%; b) 10%

21